Process for dyeing anionically modified synthetic fiber materials

ABSTRACT

Exhaustion process for dyeing anionically modified fiber materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used cationic dyestuffs of the formula [F - ( R ) Z  ] +  A -   
     in which 
     F, r, z and A -  have the meaning given below in the disclosure; by the claimed process an essentially improved exhaustion of the dyebaths is achieved.

This is a division of application Ser. No. 299,658 filed Oct. 24, 1972, now U.S. Pat. No. 3,925,015.

The invention relates to an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs; more particularly it concerns an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used as cationic dyestuffs of the formula

    [F -- (R).sub.z ] .sup.+ A.sup.-                           (I)

in which

F represents the radical of a dyestuff cation possessing at least one aromatic or hetero-aromatic ring,

R denotes a C₁ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group, preferably a C₄ -C₇ -alkyl, C₄ -C₇ -alkoxy or C₅ -C₆ -cycloalkyl group,

Z IS 1, 2 OR 3 AND

A⁻ is an anion,

With the proviso that the radical or radicals R are bonded to aromatic and/or hetero-aromatic ring systems of the dyestuff cation and that if R is a C₁ -C₂ -alkyl group, z is 3 and the 3 R are located on one and the same aromatic or hetero-aromatic ring.

As examples of R there may be mentioned: as C₁ -C₁₂ -alkyl radicals, the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-methylbutyl, pentyl-(2), pentyl-(3), n-hexyl, hexyl-(2), hexyl-(3), n-heptyl, heptyl-(2), heptyl-(3), heptyl-(4), n-octyl, octyl-(2), octyl-(3), octyl-(4), n-nonyl, nonyl-(2), n-decyl, decyl-(2), n-undecyl, undecyl-(2), n-dodecyl and dodecyl-(2) radical; as C₃ -C₁₂ -alkoxy radicals the n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert.butoxy, n-pentoxy, i-pentoxy, n-hexoxy, hexyl-(2)-oxy, n-heptoxy, heptyl-(3)-oxy, n-octyloxy, octyl-(2)-oxy, octyl-(4)-oxy, n-nonyloxy, nonyl-(2)-oxy, n-decyl, decyl-(2)-oxy, n-undecyloxy, undeycl-(2)-oxy, n-dodecyloxy and dodecyl-(2)-oxy radical; and as C₅ -C₆ -cycloalkyl radicals the cyclopentyl and cyclohexyl radical.

Possible anions A⁻ are especially the anions of inorganic or organic acids which are customary for basic dyestuffs. As examples there may be mentioned: as anions of inorganic acids, the chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate and perchlorate ion and also ZnCl₃ ^(-;) as anions of aliphatic and aromatic sulphonic acids or acid sulphuric acid esters such as the methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate and ethylsulphate ion, and as anions of organic acids the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid and suberic acid.

Dyestuffs of the formula I in which the radical R contains 4 to 7 C atoms, for example dyestuffs which contain one to three tert.-butyl or heptyl-(3) radicals, are preferred.

Dyestuffs which have proved particularly valuable are those of the formula I wherein the dyestuff cation

    [F -- (R).sub.z ] .sup.+

is

A. a dyestuff cation of the formula ##SPC1##

in which

R₁ denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

R₂ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R₃ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R₄ denotes halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl,

N,n-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl,

trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

y represents --CH= or -N= and

G represents the radicals ##SPC2##

in which

R'₁ denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

R'₂ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R'₃ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R'₄ denotes halogen, alkyl, cycloalkyl, aralkykl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

R₅ represents halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

R₆ denotes hydrogen; a lower alkyl which is optionally substituted, for example by C₁ -C₅ -carbalkoxy or C₁ -C₅ -alkoxy; an alkyl radical which in the o-position of the ring B, if a = o, can close a 5-membered or 6-membered ring, the heterocyclic ring thereby formed being optionally alkyl-substituted or condensed with a further carbocyclic ring; cycloalkyl, aralkyl or C₁ -C₅ -alkenyl;

R₇ is hydrogen; alkyl, which can optionally close a 5-membered or 6-membered ring to the adjacent o-position of the ring B, the heterocyclic ring thereby formed being optionally alkyl-substituted or fused to a further carbocyclic ring; cycloalkyl; aralkyl or aryl;

R₈ hydrogen, alkyl or aralkyl; R₇ and R₈ can further, with the nitrogen atom, close a heterocyclic ring which can optionally contain further hetero-atoms;

R₉ hydrogen, alkyl, alkoxy or halogen,

R₁₀ hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R₁₁ alkyl, aryl, carboxylic acid ester or an optionally substituted carbonamide group;

R₁₈ hydrogen, nitrile, carboxylic ester or carbonamide,

X represents -CH₂ - or 0,

a represents the numbers 0 to 1 and

m, n and p independently of one another represent a number from 0 to 3,

with the proviso that at least one of the substituents R₄, R₄ ', R₅, R₉ or R₁₁ is a C₃ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group or R₄, R₄ ' or R₅ is a C₁ -C₂ -alkyl group, in which case n, p or m have the value 3.

Dyestuffs of the formula II in which R₄ represents a t-butyl group in the 5-position and/or R₅ represents a t-butyl group in the p-position and/or R₉ represents a t-butyl group in the 5-position are particularly preferred.

B. A dyestuff cation of the formula ##SPC3##

in which

R₁₂ represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R₁₃ represents hydrogen, alkyl, cycloalkyl, or aralkyl, or R₁₂ and R₁₃ together with the nitrogen atom form a heterocyclic ring which can optionally contain further hetero-atoms,

R₁₄ can represent hydrogen, halogen, alkoxy, aralkoxy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, nitrile, trifluoromethyl, carboxylic acid ester, optionally N-substituted carbonamide groups, acyl, alkylsulphonyl or arylsulphonyl or ##EQU1## with R₁₅ and R₁₆ having the meaning given below, and K represents the radicals ##SPC4##

in which

R₉, r₁₀ and R₁₁ have the abovementioned meanings;

R₁₅ represents hydrogen, alkyl, cycloalkyl or aralkyl,

R₁₆ represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl or

R₁₅ and R₁₆, together with the nitrogen atom, form a heterocyclic ring which can optionally contain further hetero-atoms; and

R₁₇ denotes hydrogen, halogen, alkyl or alkoxy, with the proviso that at least one of the substituents R₉, R₁₁, R₁₄ or R₁₇ is a C₃ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group.

Dyestuffs of the formula III in which either R₁₄ represents a tert. butyl group in the p-position and/or R₉ represents a tert. butyl group in the 5-position are particularly preferred.

The aromatic carbocyclic rings of the dyestuff cations II and III can be fused to carbocyclic rings and can also contain, additionally to the substituents R₄, R₄ ', R₅, R₉, R₁₄ and R₁₇, further non-ionic substituents such as fluorine, chlorine or bromine atoms and also methyl, ethyl, methoxy, carbomethoxy, nitro and nitrile groups.

The aryloxy, aralkoxy, carbaralkoxy and aralkyl radicals can be substituted in the aromatic radical, especially by lower alkyl, halogen, such as fluorine, chlorine or bromine, alkoxy, carboalkoxy, nitrile, nitro and/or hydroxyl.

As examples of the groups or radicals named in the definitions, there may be mentioned:

As lower alkyl groups: C₁ -C₅ -alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, t-butyl and iso-amyl.

As alkyl groups: C₁ -C₁₂ -alkyl groups, such as have been listed for R, and also lower substituted alkyl radicals such as the 2-cyanoethyl, 2-chloroethyl and 2-hydroxyethyl radical;

Alkoxy represents methoxy, ethoxy or larger alkoxy radicals, such as are described for the radical R;

Carbalkoxy in particular represents carbomethoxy, carboethoxy, carbopropoxy and carbobutoxy;

Acyl radicals are especially the acetyl, propionyl, benzoyl and toluyl radical;

Suitable acylamino radicals are, for example, the formylamino, acetylamino, n-propionylamino, benzoylamino, 4-chlorobenzoylamino and 4-methylbenzoylamino radical.

As examples of aralkyl radicals there may be mentioned: the benzyl, β-phenylethyl and α,α-dimethylbenzyl radical as well as their derivatives substituted in the phenyl nucleus.

As cycloalkyl, cyclohexyl is of particular importance.

Aryl represents carbocyclic aromatics with 6-10 carbon atoms such as phenyl and naphthyl and their derivatives such as 4-methylphenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl and 2-methyl-4-chloro-phenyl.

N-alkyl-carbamoyl and N,N-dialkyl-carbamoyl represent, for example, methyl-carbamoyl, N-ethyl-carbamoyl, N-n-butyl-carbamoyl, N,N-dimethyl-carbamoyl, N,N-diethyl-carbamoyl and N-methyl-N-ethyl-carbamoyl.

N-alkyl-N-aryl-carbamoyl represents, for example, N-methyl-N-phenyl-carbamoyl and N-ethyl-N-phenyl-carbamoyl.

N-alkyl-sulphamoyl and N,N-dialkyl-sulphamoyl represent, for example, N-methyl-sulphamoyl, N-ethyl-sulphamoyl, N,N-dimethyl-sulphamoyl and N,N-diethyl-sulphamoyl.

As aryloxy radicals there should be mentioned, for example: the phenoxy and naphthoxy radical and their derivatives which are substituted in the aromatic ring.

Suitable aralkoxy radicals are, for example, benzyloxy, phenylethoxy, α,α-dimethylbenzyloxy and their derivatives which are optionally substituted in the phenyl nucleus.

Carbaralkoxy radicals are, for example, carbobenzoxy, carbo-α-phenylethoxy, carbo-(β-phenylethoxy) and carbo-(γ-phenyl-n-propoxy) radicals and their derivatives substituted in the phenyl nucleus.

The dyestuffs to be used according to the invention are manufactured in accordance with processes which are in themselves known. These are described, for example, in German Patent Specifications 686,198 and 742,039 or British Patents 840.282, 875.995 or 1.139.407. be used according to the invention, are added to the halogenated hydrocarbon dye baths can vary within wide limits depending on the desired depth of colour; in general, amounts of 0.1-8 per cent by weight, relative to the weight of the material to be dyed which is employed, have proved successful.

It has proved advantageous to add to the halogenated hydrocarbon dyeing liquors small amounts, for example 0.1-4, preferably 0.1-2, % by weight of water, relative to the weight of the halogenated hydrocarbon. At the same time it has proved advantageous also to add to the halogenated hydrocarbon solutions, for distribution of the water, emulsifiers in an amount of 0.1-2% by weight relative to the weight of the halogenated hydrocarbon. Possible emulsifiers are preferably non-ionic compounds; oxethylation products of fatty alcohols, phenols, fatty acid amides and fatty acids, as well as their mixtures, have proved successful.

The anionically modified synthetic fibre materials to be dyed according to the invention are in particular polyacrylonitrile modified by carboxyl and/or sulphonic acid groups, polyesters modified by carboxyl and/or sulphonic acid groups, such as polyethylene terephthalate, polycyclohexanedimethylene terephthalate, heterogeneous polyesters of terephthalic acid, isophthalic acid and ethylene glycol or of terephthalic acid, sulphoisophthalic acid and ethylene glycol, and also copolyether-ester fibres from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, or polyamides such as polyhexamethylene adipate, polycaprolactam or poly-ω-aminoundecanoic acid, modified by sulphonic acid groups. These anionically modified, synthetic fibre materials can, during dyeing, also be present as a mixture with unmodified synthetic fibre materials. The unmodified fibre component is not dyed by the cationic dyestuffs and can subsequently be dyed with another non-cationic dyestuff.

Dyeing of the anionically modified, synthetic fibre materials from chlorinated hydrocarbon solutions, which is preferably effected in closed apparatuses, can take place, for example, by introducing the fibre materials, at room temperature, into the chlorinated hydrocarbon dyeing liquors which contain the cationic dyestuffs and advantageously small amounts of water, as well as the optionally used emulsifiers, heating the bath to temperatures of 70°-140°C and keeping it at this temperature until the liquor is exhausted. After cooling, the liquor is separated off. The fibre materials are optionally briefly rinsed with fresh solvent, and are freed of the adhering solvent by suction filtration or centrifugation and subsequent drying in a stream of air.

Using the process according to the invention, it proves possible to dye anionically modified, synthetic fibre materials, in the most diverse states of processing, for example as flocks, tows, yarn, piece goods, pile fabric or made-up goods, by means of cationic dyestuffs from chlorinated hydrocarbon solutions, to give deep shades of excellent evenness. The dyeings obtained have very good rub resistance. The exhaustion of the bath is very good in the process according to the invention.

Halogenated hydrocarbons which can be used for the process according to the invention are those of boiling point between 40° and 170°C, especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane as well as aliphatic fluoro- and fluoro-chloro-hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluorotrichloroethane and trifluoropentachloropropane and aromatic chlorinated hydrocarbons and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene and 1,1,1-trichloropropane have proved particularly successful.

The cationic dyestuffs of the formula I to be used according to the invention are distinguished by good solubility in halogenated hydrocarbons, for example tetrachloroethylene.

An exhaustion process for dyeing synthetic fibre materials, containing anionic groups, by means of cationic dyestuffs from halogenated hydrocarbons is already known from British Patent 1,234,727.

The process according to the invention differs from this process in that in it cationic dyestuffs are used which possess a dyestuff cation which is soluble in chlorinated hydrocarbons, whilst according to the process of the German Offenlegungsschrift (German Published Specification) cationic dyestuffs are used which are rendered soluble in chlorinated hydrocarbon by the introduction of a lipophilic anion.

This difference in the conversion of water-soluble cationic dyestuffs into cationic dyestuffs which are soluble in chlorinated hydrocarbons is very important technologically.

Using the cationic dyestuffs to be employed according to the invention, better bath exhaustion is achieved, because of the absence of retarding anions, than with the dyestuffs described in British Pat. No. 1,234,727. As a result, no difficulties in levelling occur when dyeing with combinations of different cationic dyestuffs of the formula 1 such as is often the case when dyeing with the cationic dyestuffs described in the British Patent.

With the aid of the dyestuffs to be used according to the invention, level, reproducible dyeings are obtained in a simple manner even when dyeing with dyestuff combinations.

The parts indicated in the examples which follow are part by weight, unless otherwise stated.

EXAMPLE 1

Fibre yarn of anionically modified polyacrylonitrile is introduced, in a liquor ratio of 1:10, into a dye bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##SPC5##

1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid. The dye bath is heated in a closed dyeing machine to 100°C for 60 minutes, with vigorous agitation of the liquor. Thereafter the yarn is rinsed with fresh solvent and dried. A golden yellow dyeing of excellent fastness properties is obtained.

The dyestuff employed had been manufactured as follows: 5.2 parts of p-anisidine in 100 parts of water are diazotised, in the presence of 15.5 parts of 30% strength hydrochloric acid, with a solution of 2.95 parts of sodium nitrate in 15 parts by volume of water. After destroying the excess nitrate with amidosulphonic acid, 9.7 parts of 1,3,3-trimethyl-2-methylene-5-tertiary butyl-2,3-dihydroindole were added at 5°C. A solution of 12.5 parts of sodium acetate trihydrate in 50 parts of water was then added dropwise over the course of 1 hour. After the temperature had risen to 20°C, the resulting dyestuff was salted out. After being filtered off, it was stirred into a mixture of 200 parts by volume of chlorobenzene and 100 parts of water at 80°C, whilst at the same time keeping the pH value of the aqueous layer at pH 9-10 by adding sodium hydroxide solution. After stirring for a further 15 minutes, the organic layer was separated off, 1.7 parts of triisopropanolamine were added and dehydration was effected by distilling off about 30 parts by volume of liquid at approx. 80°C under reduced pressure. 7 parts of dimethyl sulphate were then added dropwise at 80°C and the mixture was further stirred until the methylation was complete. After stripping off the chlorobenzene in steam, the dyestuff was isolated by salting out with sodium chloride from the aqueous distillation residue.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained in the reaction of the dihydroindoles and anilines indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed.

                                      Table                                        __________________________________________________________________________              Dihydroindole               Aniline     Colour                        __________________________________________________________________________                                                      Shade                         1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-tertiary-Butylaniline                                                                           yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                2,4,5-Trimethylaniline                                                                            yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-i-Butoxyaniline  golden                                                                         yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-n-Butoxyaniline  golden                                                                         yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-(2-Methyl-butoxy)-                                                                              golden                                                      aniline            yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-Heptyl (3)-oxy-aniline                                                                          golden                                                                         yellow                        1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                p-Hexyloxy-aniline golden                                                                         yellow                        1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                    p-i-Propoxyaniline golden                        indole                                           yellow                        1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                    p-Benzyloxyaniline golden                        indole                                           yellow                        1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                    p-tertiary-Butylaniline                                                                           yellow                        indole                                                                         1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                    4-Aminodiphenyl-ether                                                                             golden                        indole                                           yellow                        1,3,3-Trimethyl-7-phenoxy-2-methylene-2,3-dihydroindole                                                      tert.-Butylaniline golden                                                                         yellow                        1,3,3-Trimethyl-5-phenoxy-2-methylene-2,3-dihydroindole                                                      tert.-Butylaniline golden                                                                         yellow                        1,3,3-Trimethyl-7-benzyloxy-2-methylene-2,3-dihydroindole                                                    tert.-Butylaniline golden                                                                         yellow                        1,3,3-Trimethyl-5-n-butoxy-2-methylene-2,3-dihydroindole                                                     p-Anisidine        golden yellow                 1,3,3-Trimethyl-5-n-butoxy-2-methylene-2,3-dihydroindole                                                     p-Toluidine        golden yellow                 1,3,3-Trimethyl-5-methyl-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1,3,3-Trimethyl-5-methoxy-2-methylene-2,3-dihydroindole                                                      4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-carbomethoxy-2-methylene-2,3-dihydro-                                                      4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-5-carboethoxy-2-methylene-2,3-dihydro-                                                       4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-5-cyclohexyl-2-methylene-2,3-dihydro-                                                        4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-5-benzyl-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1,3,3-Trimethyl-5-nitro-2-methylene-2,3-dihydroindole                                                        4-tertiary-Butylaniline                                                                           yellowish-tinged                                                               orange                        1,3,3-Trimethyl-7-methyl-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1,3,3-Trimethyl-5-trifluoromethyl-2-methylene-2,3-                                                           4-tertiary-Butylaniline                                                                           reddish-tinged                dihydroindole                                    yellow                        1,3,3-Trimethyl-7-methoxy-2-methylene-2,3-dihydroindole                                                      4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1,3,3-Trimethyl-7-chloro-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1,3,3-Trimethyl-5-chloro-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           golden yellow                 1-Ethyl-3,3-dimethyl-2-methylene-2,3-dihydroindole                                                           4-tertiary-Butylaniline                                                                           reddish-tinged                                                                 yellow                        1-Ethyl-3,3-dimethyl-5-methyl-2-methylene-2,3-dihydro-                                                       4-tertiary-Butylaniline                                                                           reddish-tinged                indole                                           yellow                        1-Ethyl-3,3-dimethyl-5-chloro-2-methylene-2,3-dihydroindole                                                  4-tertiary-Butylaniline                                                                           golden yellow                 1-Ethyl-3,3-dimethyl-5-methoxy-2-methylene-2,3-dihydroindole                                                 4-tertiary-Butylaniline                                                                           golden yellow                 1-Ethyl-3,3-dimethyl-5-carboethoxy-2-methylene-2,3-dihydro-                                                  4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1-Ethyl-3,3-dimethyl-5-cyclohexyl-2-methylene-2,3-dihydro-                                                   4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1-Ethyl-3,3-dimethyl-5-benzyl-2-methylene-2,3-dihydroindole                                                  4-tertiary-Butylaniline                                                                           golden yellow                 1-Ethyl-3,3-dimethyl-5-nitro-2-methylene-2,3-dihydroindole                                                   4-tertiary-Butylaniline                                                                           yellowish-                                                                     tinged orange                 1,3,3-Trimethyl-7-benzyl-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           reddish-                                                                       tinged yellow                 Mixture of: 1,3,3-Trimethyl-4-methyl-2-methylene-2,3-di-                                                     4-tertiary-Butylaniline                                                                           reddish-                      hydroindole and 1,3,3-trimethyl-6-methyl-2-methylene-2,3-                                                                       tinged yellow                 dihydroindole                                                                  1,3,3-Trimethyl-6,7-benzo-2-methylene-2,3,3',4',5',6'-                                                       4-tertiary-Butylaniline                                                                           yellowish-                    hexahydroindole                                  tinged orange                 1,3,3-Trimethyl-5-fluoro-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-ethoxy-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-7-ethoxy-2-methylene-2,3-dihydroindole                                                       4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-cyano-2-methylene-2,3-dihydroindole                                                        4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-acetylamino-2-methylene-2,3-dihydro-                                                       4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-5-methylsulphonyl-2-methylene-2,3-dihydro-                                                   4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-5-phenylsulphonyl-2-methylene-2,3-dihydro-                                                   4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3-Dimethyl-3-ethyl-2-methylene-2,3-dihydroindole                                                           4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-6,7-benzo-2-methylene-2,3-dihydroindole                                                      4-tertiary-Butylaniline                                                                           yellowish-                                                                     tinged orange                 1,3,3-Trimethyl-5-sulphonamido-2-methylene-2,3-dihydroindole                                                 4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-carbonamido-2-methylene-2,3-dihydroindole                                                  4-tertiary-Butylaniline                                                                           golden yellow                 1,3,3-Trimethyl-5-carboxylic acid ethylanilide-2-methylene-                                                  4-tertiary-Butylaniline                                                                           golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-7-ethyl-2-methylene-2,3-dihydroindole                                                        4-tertiary-Butylaniline                                                                           reddish-                                                                       tinged yellow                 1,3,3-Trimethyl-5-chloro-7-methoxy-2-methylene-2,3-dihydro-                                                  4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-4-chloro-7-methoxy-2-methylene-2,3-dihydro-                                                  4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-4,6-dicarbomethoxy-2-methylene-2,3-dihydro-                                                  4-tertiary-Butylaniline                                                                           golden yellow                 indole                                                                         1,3,3-Trimethyl-4,5-dichloro-7-methoxy-2-methylene-2,3-di-                                                   4-tertiary-Butylaniline                                                                           golden yellow                 hydroindole                                                                    1,3,3-Trimethyl-5-chloro-4,7-dimethoxy-2-methylene-2,3-di-                                                   4-tertiary-Butylaniline                                                                           golden yellow                 hydroindole                                                                    1,3,3,4,5,7-Hexamethyl-2-methylene-2,3-dihydroindole                                                         4-tertiary-Butylaniline                                                                           reddish-                                                                       tinged yellow                 1,3,3,4,6,7-Hexamethyl-2-methylene-2,3-dihydroindole                                                         4-tertiary-Butylaniline                                                                           reddish-                                                                       tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                    4-Amino-4'-methyl-di-                                                                             golden yellow                 indole                        phenyl-ether                                     1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                    4-Amino-4'-ethyl-diphenyl-                                                                        golden yellow                 indole                        ether                                            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                    4-Amino-4'-tert.-butyl-                                                                           golden yellow                 indole                        diphenyl-ether                                   1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-4'-cyclohexyl-diphenyl-ether                                                              golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-2'-methyl-diphenyl-ether                                                                  golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-3'-methyl-diphenyl-ether                                                                  golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-4'-methoxy-diphenyl-ether                                                                 golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            4-Amino-3'-methoxy-diphenyl-ether                                                                 golden yellow                 dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-4'-ethoxy-diphenyl-ether                                                                  golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            4-Aminophenyl-α-naphthyl-ether                                                              golden yellow                 dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            4-Aminophenyl-β-naphthyl-ether                                                               golden yellow                 dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            4-Amino-2',3',5'-trimethyl-ether                                                                  golden yellow                 dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            4-Aminodiphenylmethane                                                                            golden yellow                 dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            Aniline            reddish-                      dihydroindole                                    tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            p-Toluidine        reddish-                      dihydroindole                                    tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            m-Toluidine        reddish-                      dihydroindole                                    tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            o-Anisidine        yellow                        dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                            o-Phenetidine      yellow                        dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               p-Phenetidine      golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               4-Aminoacetanilide golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               N-Benzoyl-p-phenylene-                                                                            golden yellow                                               diamine                                          1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               2,4-Dimethoxyaniline                                                                              golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               2,5-Dimethoxyaniline                                                                              golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               3,4-Dimethoxyaniline                                                                              orange                        1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               2-Chloro-4-aminoanisole                                                                           golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               2,4,5-Trimethylaniline                                                                            reddish-                                                                       tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               2,3,5-Trimethylaniline                                                                            reddish-                                                                       tinged yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               5-Amino-2-acetylamino-                                                                            orange                                                      anisole                                          1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               6-Amino-3-methoxy- golden yellow                                               toluene                                          1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               3,4-Dicyanoaniline golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               p-Sulphanilic acid golden yellow                                               amide                                            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               4-Aminobenzamide   golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               4-Chloroaniline    golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               4-Fluoroaniline    golden yellow                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dinydroindole                                               1,2,3,4-Tetrahydro-5-                                                                             golden yellow                                               aminonaphthalene                                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                               4-Amino-2,5-diethoxy-                                                                             orange                                                      benzoic acid anilide                             1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Amino-2-methyl-5-methoxybenzanilide                                                             yellowish-                    2,3-dihydroindole                                tinged orange                 1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                4-Cyclohexylaniline                                                                               golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                2,4-Diethoxyaniline                                                                               golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                2-Aminonaphthalene golden yellow                 2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                3,4-Diisopropoxyaniline                                                                           orange                        2,3-dihydroindole                                                              __________________________________________________________________________

EXAMPLE 2

A fabric of anionically modified polyamide is dyed, in accordance with the procedure indicated in Example 1, in a bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##SPC6##

1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid.

A level greenish-tinged yellow dyeing of good fastness properties is obtained.

The dyestuff had been manufactured as follows: 10 parts of 1,3,3-trimethyl-5-tertiary butyl-2-methylene-2,3-dihydroindol-ω-aldehyde and 7.8 parts of p-benzyloxyaniline were stirred with 15 parts by volume of glacial acetic acid and 5 parts of water for 4 hours at room temperature. The solution was subsequently diluted with 300 parts of water. After salt-ing out with 20 parts by weight of sodium chloride, the dyestuff was separated from the solution.

Equivalent dyeings, in the colour shades indicated in the table, on the substrates indicated in the table were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of the aldehydes and amines indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed. (PA = anionically modified polyacrylonitrile, PE anionically modified polyester).

                                      Table                                        __________________________________________________________________________     Aldehyde                      Amine            Colour Shade                                                                              Substrate            __________________________________________________________________________     1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-tert.-Butylaniline                                                                            greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      4(p-tert.Butyl)-phen-                                                                           yellow         PE                   hydroindol-ω-aldehyde                                                                              oxyaniline                                           1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-Dodecyloxyaniline                                                                             yellow         PE                   hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-Cyclohexylaniline                                                                             greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-5-benzyloxy-2-methylene-                                                                 p-tert.Butylaniline                                                                             greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2-Methyl-2,3-dihydro-                                                                           greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              indole                                               1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      p-Anisidine      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      p-tert.-Butylaniline                                                                            greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-i-Propoxyaniline                                                                              greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Butoxyaniline                                                                               greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-i-Butoxyaniline                                                                               greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      4-t-Butoxyaniline                                                                               greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-(2-Methylbutoxy)-                                                                             greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                                              aniline                                              1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Pentyloxy-aniline                                                                           greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Hexyloxy-aniline                                                                            greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-[Hexyl-(2)-oxy]-aniline                                                                       greenish-tinged                                                                               PAllow               hydroindol-ω  -aldehyde                                                  1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Heptyloxy-aniline                                                                           greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Octyloxy-aniline                                                                            yellow         PE                   hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Nonyloxy-aniline                                                                            yellow         PE                   hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Decyl-oxy-aniline                                                                           yellow         PE                   hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-n-Undecyloxyaniline                                                                           yellow         PE                   hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-[Heptyl-(3)-oxy]-aniline                                                                      greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-5-n-butoxy-2-methy-                                                                      p-Anisidine      greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-n-butoxy-2-methy-                                                                      2-Methyl-2,3-dihydroindole                                                                      greenish-tinged yellow              lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-[Pentyl-(2)-oxy]-aniline                                                                      greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      p-[Hexyl-(2)-oxy]-aniline                                                                       greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      2,3,3-Trimethyl-5-tert.-                                                                        greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                                              butyl-indoline                                       1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      2,3,3-Trimethyl-5-n-butoxy-                                                                     greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                                              indoline                                             1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2,3,3-Trimethyl-5-methoxy-                                                                      greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  indoline                                             1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2,3,3-Trimethyl-5-benzyloxy-                                                                    greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  indoline                                             1,3,3-Trimethyl-2-methylene-5.-tert-                                                                     2,3,3-Trimethyl-5-phenoxy-                                                                      greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  indoline                                             1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2,3,3-Trimethyl-7-phenoxy-                                                                      greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  indoline                                             1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      Aniline          greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      p-Toluidine      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      m-Toluidine      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      o-Anisidine      yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      m-Anisidine      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      o-Phenetidine    yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      p-Phenetidine    greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Aminoacetanilide                                                                              greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      N-Benzoyl-p-phenylenediamine                                                                    greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2,4-Dimethoxyaniline                                                                            reddish-tinged                                                                                PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2,5-Dimethoxyaniline                                                                            reddish-tinged                                                                                PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      3,4-Dimethoxyaniline                                                                            reddish-tinged                                                                                PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      3,4-Diisopropoxyaniline                                                                         reddish-tinged                                                                                PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2-Chloro-4-aminoanisole                                                                         yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2,4,5-Trimethylaniline                                                                          greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2,3,5-Trimethylaniline                                                                          greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      5-Amino-2-acetylamino-                                                                          reddish-tinged                                                                                PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              anisole                                              1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      6-Amino-3-methoxy-toluene                                                                       yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      3,4-Dicyanoaniline                                                                              yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      p-Sulphanilic acid amide                                                                        yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-benzamide                                                                               yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Chloroaniline  greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Fluoroaniline  greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      1,2,3,4-Tetrahydro-5-                                                                           yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                                              amino-naphthalene                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-2,5-diethoxy-N-                                                                         yellowish-tinged                                                                              PAange               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-2-methyl-5-                                                                             yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                                              methoxy-N-benzoylaniline                             1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Cyclohexylaniline                                                                             greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2,5-Diethoxyaniline                                                                             yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2-Amino-naphthalene                                                                             yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      1,2,3,4-Tetrahydroquinoline                                                                     greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      Hexahydrocarbazole                                                                              yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      1,2,3,4-Tetrahydro-6-                                                                           yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                                              methoxy-quinoline                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Aminodiphenylmethane                                                                          greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-4'-methyldiphenyl-                                                                      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              methane                                              1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      1-Aminodiphenyl-ether                                                                           greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      2-Aminodiphenyl-ether                                                                           greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-4'-methyl-diphenyl-                                                                     greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              ether                                                1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                      4-Amino-4'-ethyl-diphenyl-                                                                      greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              ether                                                1,3,3-Trimethyl-2-methylene-2,3-di-                                                                      4-Amino-4'-tertiary-butyl-                                                                      greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                                              diphenyl-ether                                       1,3,3-Trimethyl-5-methyl-2-methylene-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-methoxy-2-methylene-                                                                   p-tertiary-Butylaniline                                                                         yellow         PA                   2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-carbomethoxy-2-methyl-                                                                 p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-carboethoxy-2-methy-                                                                   p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-cyclohexyl-2-methylene-                                                                p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-benzyl-2-methylene-2,3-                                                                p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-nitro-2-methylene-2,3-                                                                 p-tertiary-Butylaniline                                                                         reddish-tinged                                                                                PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-7-methyl-2-methylene-2,3-                                                                p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-trifluoromethyl-2-methy-                                                               p-tertiary-Butylaniline                              dihydroindol-ωyellow                                                                               PA                                                   lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-7-methoxy-2-methylene-2,3-                                                               p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω -aldehyde                                                 1,3,3-Trimethyl-7-chloro-2-methylene-2,3-                                                                p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-chloro-2-methylene-2,3-                                                                p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1-Ethyl-3,3-dimethyl-2-methylene-2,3-di-                                                                 p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               hydroindol-ω-aldehyde                                                    1-Ethyl-3,3-dimethyl-5-methyl-2-methy-                                                                   p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-chloro-2-methy-                                                                   p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-methoxy-2-methy-                                                                  p-tertiary-Butylaniline                                                                         yellow         PA                   lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-carboethoxy-2-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1-Ethyl-3,3-dimethyl-5-cyclohexyl-2-                                                                     p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1-Ethyl-3,3-dimethyl-5-benzyl-2-methy-                                                                   p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-nitro-2-methy-                                                                    p-tertiary-Butylaniline                                                                         reddish-tinged                                                                                PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-7-benzyl-2-methylene-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              Mixture of: 1,3,3-Trimethyl-4-methyl-2-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω -aldehyde                                   and 1,3,3-trimethyl-6-methyl-2-methy-                                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-6,7-benzo-2-methylene-                                                                   p-tertiary-Butylaniline                                                                         reddish-tinged                                                                                PAllow               2,3,3',4',5',6'-hexahydroindol-ω-                                        aldehyde                                                                       1,3,3-Trimethyl-5-fluoro-2-methylene-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-ethoxy-2-methylene-                                                                    p-tertiary-Butylaniline                                                                         yellow         PA                   2,3-hydroindol-ω-aldehyde                                                1,3,3-Trimethyl-7-ethoxy-2-methylene-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-cyano-2-methylene-                                                                     p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-acetylamino-2-methy-                                                                   p-tertiary-Butylaniline                                                                         yellow         PA                   lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-methylsulphonyl-2-                                                                     p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-phenylsulphonyl-2-                                                                     p-tertiary-Butylaniline                                                                         yellow         PA                   methylene-2,3-dihydroindol-ω-aldehyde                                    1,3-Dimethyl-3-ethyl-2-methylene-2,3-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-6,7-benzo-2-methylene-                                                                   p-tertiary-Butylaniline                                                                         yellow         PA                   2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-sulphonamido-2-methy-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-carbonamido-2-methy-                                                                   p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-carboxylic acid ethyl                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               anilide-2-methylene-2,3-dihydroindol-                                          ω-aldehyde                                                               1,3,3-Trimethyl-7-ethyl-2-methylene-2,3-                                                                 p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-chloro-7-methoxy-2-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-4-chloro-7-methoxy-2-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-4,5-dichloro-7-methoxy-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2-methylene-2,3-dihydroindol-ω-aldehyde                                  1,3,3-Trimethyl-5-chloro-4,7-dimethoxy-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               2-methylene-2,3-dihydroindol-ω-aldehyde                                  1,3,3-Trimethyl-4,6-dicarbomethoxy-2-                                                                    p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3,4,5,7-Hexamethyl-2-methylene-2,3-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3,4,6,7-Hexamethyl-2-methylene-2,3-                                                                  p-tertiary-Butylaniline                                                                         greenish-tinged                                                                               PAllow               dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     3-Amino-phenyl-benzyl-                                                                          greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2-Amino-phenyl-benzyl-                                                                          greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Aminophenyl-p-methyl-                                                                         greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     3-Aminophenyl-p-methyl-                                                                         greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2-Aminophenyl-p-methyl-                                                                         yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-2-methylphenyl-                                                                         yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     5-Amino-2-methylphenyl-                                                                         yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     2-Amino-5-methylphenyl-                                                                         yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-2-methoxyphenyl-                                                                        reddish-tinged                                                                                PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-3-methoxyphenyl-                                                                        yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-3-methylphenyl-                                                                         yellow         PA                   butyl-2,3dihydroindol-ω-aldehyde                                                                   benzyl-ether                                         1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-4'-cyclohexyl-                                                                          yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  diphenyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-2'-methyl-diphenyl-                                                                     yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-3'-methyl-diphenyl-                                                                     yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-4'-methoxy-diphenyl-                                                                    greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-3'-methoxy-                                                                             yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  diphenyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-4'-ethoxy-diphenyl-                                                                     yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  ether                                                1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-4'-acetylamino-                                                                         yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  diphenyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-4'-hydroxy-                                                                             yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  diphenyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Aminophenyl-α-                                                                          greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  naphthyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Aminophenyl-β-                                                                           greenish-tinged                                                                               PAllow               butyl-2,3-dihydroindol-ω-aldehyde                                                                  naphthyl-ether                                       1,3,3-Trimethyl-2-methylene-5-tert.-                                                                     4-Amino-2',-3'-5'-                                                                              yellow         PA                   butyl-2,3-dihydroindol-ω-aldehyde                                                                  trimethyldiphenyl-                                                             ether                                                1,3,3-Trimethyl-7-phenoxy-2-methy-                                                                       p-tertiary-Butylanil-                                                                           greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                                                   ine                                                  1,3,3-Trimethyl-7-benzyloxy-2-                                                                           p-tertiary-Butyl-                                                                               greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ω-aldehyde                                                              aniline                                              1,3,3-Trimethyl-5-phenoxy-2-methy-                                                                       p-tertiary-Butyl-                                                                               greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                                                   aniline                                              1,3,3-Trimethyl-5-benzyloxy-2-methy-                                                                     p-tertiary-Butyl-                                                                               greenish-tinged                                                                               PAllow               lene-2,3-dihydroindol-ω-aldehyde                                                                   aniline                                              1,3,3-Trimethyl-5-carbobenzoxy-2-                                                                        p-tertiary-Butyl-                                                                               greenish-tinged                                                                               PAllow               methylene-2,3-dihydroindol-ωaniline                                      aldehyde                                                                       __________________________________________________________________________

EXAMPLE 3

Dyeing is carried out as described in Example 1, but instead of the dyestuff described there the same amount of the dyestuff of the formula ##SPC7##

is used. A bluish-tinged red dyeing of uniform strength and excellent wet fastness properties is obtained.

The dyestuff had been obtained as follows: 7 parts of 1,3,3-trimethyl-5-tertiary butyl-2-methylene-2,3-dihydroindole and 5.5 parts of 4-diethylamino-benzaldehyde in 15 parts by volume of glacial acetic acid were stirred for 3 hours at 100°C. The dyestuff melt was then poured into 300 parts of water and the dyestuff was salted out with 20 parts of sodium chloride, separated from the solution and dried.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained on polyacrylonitrile textile materials if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of 1,3,3-trimethyl-5-tert.-butyl-2-methylene-2,3-dihydroindole with the aldehydes indicated in the table was employed.

                  Table                                                            ______________________________________                                         Aldehyde                 Colour shade                                          ______________________________________                                         p-Dimethylamino-benzaldehyde                                                                            bluish-tinged                                                                  red                                                   p(2-Chloroethyl-butyl-amino)-benzaldehyde                                                               red-violet                                            N-methyl-p-ethoxy-diphenylamine-(4)-aldehyde                                                            reddish-tinged                                                                 violet                                                N-ethylcarbazolaldehyde  orange                                                1-Methyl-2-phenylindol-3-aldehyde                                                                       orange                                                1-Methyl-2-phenyl-5-tertiary butyl-indol-3-                                                             orange                                                aldehyde                                                                       ______________________________________                                    

Equivalent dyeings, in the colour shades indicated in the table, were also obtained on anionically modified polyacrylonitrile if instead of the dyestuff employed the same amount of one of the dyestuffs obtained on reaction of the aldehydes and dihydroindoles listed in the table, under the manufacturing conditions described for the dyestuff used, was employed.

                  Table                                                            ______________________________________                                                                        Colour                                          Aldehyde    Dihydroindole      shade                                           ______________________________________                                         1-Methyl-2-phenyl-                                                                         1,3,3-trimethyl-5-n-butyloxy-                                                                     orange                                          indol-3-aldehyde                                                                           2-methylene-2,3-dihydroindole                                      1-n-Butyl-2-phenyl-                                                                        1,3,3-trimethyl-5-tertiary                                                                        orange                                          indol-3-aldehyde                                                                           butyl-2-methylene-2,3-dihydro-                                                 indole                                                             1-Isobutyl-2-phenyl-                                                                       1,3,3-trimethyl-5-tertiary                                                                        orange                                          indol-3-aldehyde                                                                           butyl-2-methylene-2,3-dihydro-                                                 indole                                                             ______________________________________                                    

EXAMPLE 4

A fabric of anionically modified polyester fibres (Dacron 64) is dyed, in accordance with the procedure indicated in Example 1, in a bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##SPC8##

1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid.

A uniform green dyeing of good wet fastness properties is obtained.

The dyestuff had been manufactured as follows: 15 parts of 4-diethylamino-4'-tert.-butyl-benzophenone, 11 parts of N-methyl-p-ethoxydiphenylamine and 30 parts of phosphorus oxychloride were stirred, 10 parts of phosphorus pentoxide were then added and the mixture was heated to 100°C for 2 hours. The melt was introduced into 500 parts of water, and stirred therein until the phosphorus oxychloride was decomposed. After adding 30 parts of sodium chloride, the dyestuff was filtered off.

If instead of 4-diethylamino-4'-tert.-butyl-benzophenone the equivalent amount of 4-phenylmethylamino-5-tertiary butyl-benzophenone was employed, a dyestuff was obtained with which an even yellowish-tinged green dyeing also having excellent fastness properties was obtained.

EXAMPLE 5

A fabric of polyacrylonitrile fibres is dyed in accordance with the procedure described in Example 1 with the dyestuff of the formula ##SPC9##

A uniform, blue-green dyeing of good fastness properties is obtained.

The dyestuff had been manufactured as follows: 15 parts of 4-tert.-butyl-4'-diethylamino-benzophenone, 10 parts of 1-methyl-2-phenylindole and 30 parts of phosphorus oxychloride were stirred for 4 hours at 100°C. The melt was then poured into 400 parts of water and stirred until the phosphorus oxychloride was decomposed. After adding 20 parts of sodium chloride, the dyestuff was filtered off and dried.

Equivalent dyeings in the colour shades indicated in the table, on the substrate indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of the benzophenones and indoles indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed (PA = anionically modified polyacrylonitrile, PE = anionically modified polyester).

                                      Table                                        __________________________________________________________________________     Benzophenone        Indole           Colour shade                                                                              Substrate                      __________________________________________________________________________     4-Diethylamino-4-tertiary-butyl-                                                                   1,2-Dimethylindole                                                                              strongly reddish-                                                                         PA                             benzophenone                         tinged blue                               4-Di-n-propylamino-4-tertiary                                                                      1,2-Dimethylindole                                                                              reddish-tinged                                                                            PE                             butyl-benzophenone                   blue-grey                                 4-Di-n-propylamino-4-tertiary                                                                      1-Methyl-2-phenylindole                                                                         bluish-tinged                                                                             PE                             butyl-benzophenone                   grey-green                                4-N-phenyl-N-methylamino-4-                                                                        1,2-Dimethylindole                                                                              reddish-tinged                                                                            PE                             tertiary butyl-benzophenone          grey-blue                                 4-N-phenyl-N-methylamino-4-                                                                        1 Methyl-2-phenylindole                                                                         green      PE                             tertiary butyl-benzophenone                                                    4-Diethylaminobenzophenone                                                                         1-Ethyl-2-phenyl-5-tertiary                                                                     greenish-tinged                                                                           PE                                                 butylindole      blue                                      4-Diethylamino-2-chlorobenzo-                                                                      1-Ethyl-2-phenyl-5-tertiary                                                                     greenish-tinged                                                                           PE                             phenone             butylindole      blue                                      4-Phenylmethylamino-benzophenone                                                                   1-Ethyl-2-phenyl-5-tertiary                                                                     blue-green PE                                                 butylindole                                                4-Diethylamino-benzophenone                                                                        1-Dodecyl-2-phenylindole                                                                        blue-grey  PE                             4,4'-Bis-diethylaminobenzo-                                                                        1-Dodecyl-2-phenylindole                                                                        reddish-tinged                                                                            PE                             phenone                              blue                                      4-Dimethylamino-4'-tertiary                                                                        1,2-Dimethylindole                                                                              strongly reddish-                                                                         PA                             butyl-benzophenone                   tinged blue                               4-Dimethylamino-4'-tertiary                                                                        1-Methyl-2-phenylindole                                                                         greenish-tinged                                                                           PA                             butyl-benzophenone                   blue                                      4-Diethylamino-4'-methoxy-                                                                         1-Ethyl-2-phenyl-5-tert.-                                                                       black-grey PE                             benzophenone        butylindole                                                4-Dimethylamino-4'-methoxy-                                                                        1-Ethyl-2-phenyl-5-tert.-                                                                       reddish-tinged                                                                            PA                             benzophenone        butylindole      grey                                      4-N(p-Ethoxy-phenyl)N-methylamino-                                                                 1-Ethyl-2-phenyl-5-tert.-                                                                       green      PE                             benzophenone        butylindole                                                4-Aminobenzophenone 1-Ethyl-2-phenyl-5-tert.-                                                                       bluish-tinged red                                                                         PA                                                 butylindole                                                4-Aminobenzophenone 1-Dodecyl-2-phenylindole                                                                        claret     PE                             __________________________________________________________________________

EXAMPLE 5

Polyacrylonitrile fibre yarn is dyed in accordance with the procedure indicated in Example 1 with the dyestuff of the formula ##SPC10##

A bluish-tinged red dyeing of good wet fastness properties is obtained.

The dyestuff had been obtained by heating equimolar amounts of 1,3,3-trimethyl-5-t.-butyl-2-methylene-2,3-dihydroindole-ω-aldehyde and 1,3,3-trimethyl-2-methylene-2,3-dihydroindole, in the same amount by weight of a mixture of 75% of glacial acetic acid and 25% of acetic anhydride, to 100°C for 5 hours, subsequently stirring the mixture with a 20-fold amount of water, and salting out with sodium chloride.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs which are obtained in the reaction of the dihydroindoles indicated in the table with 1,3,3-trimethyl-5-tert.-butyl-2-methylene-2,3-dihydroindol-ω-aldehyde, under the manufacturing conditions described for the dyestuff used, was employed.

                                      Table                                        __________________________________________________________________________     Dihydroindole                      Colour shade                                __________________________________________________________________________     1,3,3-Trimethyl-2-methylene-5-methoxy-ω-cyano-2,3-dihydroindole                                          bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-chloro-2,3-dihydroindole                                                         bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-methyl-2,3-dihydroindole                                                         bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-cyano-2,3-dihydroindole                                                          bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-carbomethoxy-2,3-dihydroindole                                                   bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-methoxy-2,3-dihydroindole                                                        bluish-tinged red                              1,3,3-Trimethyl-2-methylene-7-methyl-2,3-dihydroindole                                                         bluish-tinged red                              1,3,3-Trimethyl-2-methylene-7-chloro-2,3-dihydroindole                                                         bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-tert.-butyl-2,3-dihydroindole                                                    bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-methyl-sulphonyl-2,3-dihydroindole                                               bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-nitro-2,3-dihydroindole                                                          strongly bluish-tinged red                     __________________________________________________________________________ 

I claim:
 1. In the process of dyeing an anionically modified fiber material by exhaustion from a dyebath consisting essentially of a cationic dyestuff dissolved in halogenated hydrocarbon the improvement comprising the use as said cationic dyestuff a dyestuff soluble in said halogenated hydrocarbon and having the formula ##SPC11##in which A⁻ is a non-lipophilic anion; R₁ is hydrogen; C₁ -C₁₂ -alkyl; C₁ -C₅ -alkyl substituted with CN, Cl or OH; cycloalkyl, aralkyl or aryl; R₂ is C₁ -C₅ -alkyl, cycloalkyl or aralkyl; R₃ is C₁ -C₅ -alkyl, cycloalkyl or aralkyl; R₄ is halogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbalkoxy; y is CH or N; and G is ##SPC12##in which R'₁ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, cycloalkyl, aralkyl or aryl; R'₂ is C₁ -C₅ -alkyl, cycloalkyl or aralkyl; R'₃ is C₁ -C₅ -alkyl, cycloalkyl or aralkyl; R'₄ is halogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy; R₇ is hydrogen; C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, which can optionally close a 5-membered or 6-membered ring to the adjacent o-position of the ring B, the heterocyclic ring thereby formed being optionally alkyl substituted or fused to a further carbocyclic ring; cycloalkyl; aralkyl or aryl; R₈ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, or aralkyl; R₇ and R₈ can further, with the nitrogen atom, close a heterocyclic ring which can optionally contain further hetero atoms; R₉ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, alkoxy or halogen; R₁₀ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aralkyl, cycloalkyl or aryl; R₁₁ is C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aryl, carboxylic acid ester, carbonamide or substituted carbonamide R₁₈ is hydrogen, nitrile, carboxylic ester or carbonamide; X is --CH₂ -- or O; a is 0 or 1; and m, n and p independently of one another are numbers from 0 to 3; "aryl" is phenyl; naphthyl; 4-methyl-phenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl, or 2-methyl-chlorophenyl; "aralkyl" is benzyl, β-phenethyl or α,α-dimethylbenzyl; or the foregoing substituted in the phenyl nucleus by lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; "aryloxy" is phenoxy or naphthoxy or the foregoing substituted with lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; "substituted carbonamide" is methyl-carbamoyl, N-ethyl-carbamoyl, N-n-butyl-carbamoyl, N,N-dimethyl-carbamoyl, N,N-diethyl-carbamoyl, N-methyl-N-ethyl-carbamoyl, N-methyl-N-phenyl-carbamoyl or N-ethyl-N-phenyl-carbamoyl; "carboxylic acid ester" is selected from the group consisting of carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, carbobenzoxy, carbo-α-phenylethoxy, carbo-(β-phenylethoxy) and carbo-(γ-phenyl-n-propoxy) radicals and their derivatives substituted in the phenyl nucleus with lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; with the proviso that at least one of the substituents R₄, R₄ ', R₉ or R₁₁ is a C₃ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group or R₄ or R₄ ' is a C₁ -C₂ -alkyl group, in which case n, p or m have the value
 3. 2. In the process of dyeing an anionically modified fiber material by exhaustion from a dyebath consisting essentially of a cationic dyestuff involved in halogenated hydrocarbon the improvement comprising the use as said cationic dyestuff a dyestuff soluble in said halogenated hydrocarbon and having the formula ##SPC13##in which A⁻ is a non-lipophilic anion; R₁₂ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aralkyl, cycloalkyl or aryl; R₁₃ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, cycloalkyl or aralkyl, or R₁₂ and R₁₃ together with the nitrogen atom form a heterocyclic ring which can optionally contain further hetero-atoms; R₁₄ is hydrogen, halogen, alkoxy, aralkoxy, aryloxy, acyloxy, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aralkyl, aryl, nitro, nitrile, trifluoromethyl, carboxylic acid ester, optionally N-substituted carbonamide groups, ##EQU2## acyl, alkylsulphonyl or arylsulphonyl or K is ##SPC14##or R₉ is hydrogen, C₁ -C₁ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, alkoxy or halogen; R₁₀ is hydrogen, C_(1-C) ₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aralkyl, cycloalkyl or aryl; R₁₁ is C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aryl, carboxylic acid ester, carbonamide or substituted carbonamide; R₁₅ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, cycloalkyl or aralkyl; R₁₆ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, aralkyl, cycloalkyl or aryl; or R₁₅ and R₁₆, together with the nitrogen atom, form a heterocyclic ring which can optionally contain further hetero atoms; R₁₇ is hydrogen, halogen, C₁ -C₁₂ -alkyl, C₁ -C₅ -alkyl substituted with CN, Cl or OH, or alkoxy; "aryl" is phenyl; naphthyl; 4-methyl-phenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl, or 2-methyl-chlorophenyl; "aralkyl" is benzyl, β-phenethyl, or α,α-dimethylbenzyl; or the foregoing substituted in the phenyl nucleus by lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; "aryloxy" is phenoxy or naphthoxy or the foregoing substituted with lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; "substituted carbonamide" is methyl-carbamoyl, N-ethyl-carbamoyl, N-n-butyl-carbamoyl, N,N-dimethyl-carbamoyl, N,N-diethyl-carbamoyl, N-methyl-N-ethyl-carbamoyl, N-methyl-N-phenyl-carbamoyl or N-ethyl-N-phenyl-carbamoyl; "carboxylic acid ester" is selected from the group consisting of carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy, carbobenzoxy, carbo-α-phenylethoxy, carbo-(β-phenylethoxy) and carbo-(γ-phenyl-n-propoxy) radicals and their derivatives substituted in the phenyl nucleus with lower alkyl, halogen, alkoxy, carboalkoxy, nitro, cyano or hydroxyl; with the proviso that at least one of the substituents R₉, R₁₁, R₁₄ or R₁₇ is C₃ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy, or C₅ -C₆ -cycloalkyl or R₁₀ is C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl.
 3. Process of claim 1 in which said non-lipophilic anion is chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphate, phosphate, dihydrogenophosphate, nitrate, perchlorate, ZnCl₃ ⁻, methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate, ethylsulphate or the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid or suberic acid.
 4. Process of claim 2 in which said non-lipophilic anion is chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate, perchlorate, ZnCl₃ ⁻, methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate, ethylsulphate or the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid or suberic acid.
 5. Process of claim 1 in which said dyebath also contains 0.1 to 4 percent by weight of water relative to the weight of the halogenated hydrocarbon.
 6. Process of claim 2 in which said dyebath also contains 0.1 to 4 percent by weight of water relative to the weight of the halogenated hydrocarbon. 